JP2013095870A - Color filter coloring agent, coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter coloring agent having a high contrast ratio and excellent coloring power.SOLUTION: The color filter coring agent comprises a specific quinophthalone compound, for example, a compound having a quinaldine nucleus bonded to a phthalimide group, obtained by condensing formula (7), a phthalic anhydride and a naphthalic anhydride, or comprises a compound having a phthaloyl group to which a ring is condensed.

Description

  The present invention relates to a color liquid crystal display device, a color filter colorant used in the production of a color filter used for a color image pickup tube element, a color composition, and a color filter formed using the same. .

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. The demand for higher brightness and higher color reproducibility is increasing.

  A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in In general, it is often formed of three color filter segments of red, green, and blue. Each segment is as fine as several microns to several hundreds of microns, and is arranged in a predetermined arrangement for each hue. .

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent heat resistance and light resistance as a colorant is mainly used.

  In the production of the green filter segment, a yellow pigment is used as a toning colorant. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment Yellow 185 and the like are mainly used. Among them, C.I. has a high transmittance. I. Pigment Yellow 138 is often used. However, C.I. I. Although pigment yellow 138 is relatively excellent in brightness, further improvement in brightness is desired. In recent years, there has been a strong demand for high contrast for color filters. I. Pigment Yellow 138 has a problem of low contrast. Therefore, the conventional C.I. I. There is a demand for a yellow colorant that is superior in brightness and contrast to CI Pigment Yellow 138.

  On the other hand, examples of the quinophthalone compound include C.I. I. Pigment dispersants for stabilizing the dispersion of Pigment Yellow 138 are known. For example, Patent Document 1 discloses a quinophthalone compound containing a sulfonic acid, and Patent Document 2 discloses a quinophthalone compound to which a phthalimidomethyl group is added. All of these are C.I. I. A pigment dispersant for facilitating the dispersion of CI Pigment Yellow 138, and by using these pigment dispersants, C.I. I. Although the dispersibility of Pigment Yellow 138 is improved, the contrast ratio has not yet achieved the desired characteristics.

  Patent Document 3 discloses a quinophthalone compound using the following compound (1) as a starting material as a pigment composition with improved dispersion stability over time.

  Patent Document 4 describes that a pigment composition excellent in coloring power, sharpness and the like can be obtained by using a compound in which a quinophthalone structure is dimerized.

  However, the colorants containing these quinophthalone compounds are not sufficiently improved in problems such as contrast ratio and insufficient coloring power when used for color filters.

  Patent Document 5 discloses a quinophthalone compound having a naphthalene ring for coloring a polymer material. However, all of the quinophthalone compounds obtained by the method of Patent Document 5 are for the purpose of coloring plastics, and their suitability for color filter applications is unknown.

  Patent Document 6 discloses a quinophthalone compound having a 1,2-naphthylene group, a 2,3-naphthylene group, a 1,8-naphthylene group, or a 2,2′-biphenylene group. However, all the quinophthalone compounds obtained by the method of Patent Document 6 are mainly intended for coloring plastics, and their suitability for color filter applications is unclear.

JP 2002-179799 A JP 2008-95007 A JP 2008-81566 A JP 2008-74985 A JP-A 51-147544 JP 51-150438 A

  An object of the present invention is to provide a color filter coloring agent, a coloring composition, and a color filter using the same, which have excellent coloring power and can obtain high brightness and high contrast ratio when used in a color filter. It is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have excellent dispersibility and coloring power when used as a color filter colorant containing a quinophthalone compound having a specific structure. The present inventors have found that a color filter that gives high brightness and contrast ratio can be produced, and have reached the present invention.

  That is, this invention relates to the coloring agent for color filters characterized by containing the quinophthalone compound represented by following General formula (1).

［一般式（１）中、Ｒ¹〜Ｒ⁵は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有しても良いアルキル基、置換基を有しても良いアルコキシル基、置換基を有しても良いアリール基、−ＳＯ₃Ｈ；−ＣＯＯＨ；およびこれら酸性基の１価〜３価の金属塩；アルキルアンモニウム塩、置換基を有しても良いフタルイミドメチル基、または置換基を有しても良いスルファモイル基を示し、ＹおよびＺは、ハロゲン原子、置換基を有しても良いアルキル基、置換基を有しても良いアルコキシル基、置換基を有しても良いアリール基、−ＳＯ₃Ｈ；−ＣＯＯＨ；およびこれら酸性基の１価〜３価の金属塩；アルキルアンモニウム塩、置換基を有しても良いフタルイミドメチル基、並びに置換基を有しても良いスルファモイル基からなる群から選ばれた置換基を有してもよいアリーレン基を示し、ＹおよびＺのうち少なくとも１つは、ハロゲン原子、置換基を有しても良いアルキル基、置換基を有しても良いアルコキシル基、置換基を有しても良いアリール基、−ＳＯ₃Ｈ；−ＣＯＯＨ；およびこれら酸性基の１価〜３価の金属塩；アルキルアンモニウム塩、置換基を有しても良いフタルイミドメチル基、並びに置換基を有しても良いスルファモイル基からなる群から選ばれた置換基を有してもよい１，８−ナフチレン基を示す。］

[In General Formula (1), R ^{1 to} R ⁵ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. An aryl group that may have, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts, phthalimidomethyl groups that may have a substituent, or substituents; Sulfamoyl group which may have, Y and Z are a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent , —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts, optionally substituted phthalimidomethyl groups, and optionally substituted sulfamoyl groups From the group of An arylene group optionally having a substituent, wherein at least one of Y and Z is a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, An aryl group which may have a substituent, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts, an optionally substituted phthalimidomethyl group, and 1 shows a 1,8-naphthylene group which may have a substituent selected from the group consisting of sulfamoyl groups which may have a substituent. ]

  The present invention also relates to the colorant for a color filter, wherein the quinophthalone compound is any one of the following general formulas (1A) to (1C).

[In the general formulas (1A) to (1C), R ^{6 to} R ²⁰ , R ^{21 to} R ³⁷ , and R ^{38 to} R ⁵² may each independently have a hydrogen atom, a halogen atom, or a substituent. An alkyl group, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts , A phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent, wherein adjacent groups of R ^{11 to} R ¹⁴ and R ^{49 to} R ⁵² are combined to form a substituent. An aromatic ring which may have a group may be formed. ]

The present invention also relates to the colorant for a color filter, wherein R ^{11 to} R ²⁰ , R ^{26 to} R ³⁷ , and R ^{43 to} R ⁵² are each independently a hydrogen atom or a halogen atom.

  The present invention also relates to the color filter colorant further comprising a yellow colorant.

  In the present invention, the yellow colorant is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, and C.I. I. The color filter colorant as described above, which is at least one selected from CI Pigment Yellow 185.

  The present invention also relates to a color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant is the colorant. .

  Further, the present invention relates to the color filter coloring composition, further comprising a green colorant and / or a blue colorant.

  Further, the present invention relates to the color composition for color filters, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  In the color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, at least one green filter segment is formed by the color filter coloring composition. Relates to the color filter.

  According to the present invention, by using the quinophthalone compound represented by the general formula (1) as a color filter colorant, the color filter colorant having high brightness and high contrast ratio and excellent coloring power, A coloring composition and a color filter using the same can be provided.

  Hereinafter, the present invention will be described in detail. In this specification, “CI” means a color index.

<Colorant>
The colorant for color filters containing the quinophthalone compound represented by the general formula (1) of the present invention (sometimes simply referred to as “colorant”) will be described. The colorant of the present invention is characterized by containing a quinophthalone compound represented by the general formula (1). First, the substituent of R < ¹ > -R < ⁵ > in General formula (1) is demonstrated.

  Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

  Examples of the alkyl group which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, and n-octyl. Group, stearyl group, linear or branched alkyl group such as 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4 Examples include alkyl groups having a substituent such as -methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group.

  Examples of the alkoxyl group which may have a substituent include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutyloxy group, tert-butyloxy group, neopentyloxy group, 2, 3 -In addition to linear or branched alkoxyl groups such as dimethyl-3-pentoxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro Examples include an alkoxyl group having a substituent such as a propoxy group and a benzyloxy group.

  In addition, examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group, an anthranyl group, a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p- Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and other aryl groups having a substituent.

Examples of acidic groups include —SO ₃ H and —COOH, and monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, and aluminum salts. Etc. In addition, as the alkyl ammonium salt of acidic group, quaternary alkyl such as ammonium salt of long-chain monoalkylamine such as octylamine, laurylamine, stearylamine, palmityltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salt, etc. An ammonium salt is mentioned.

The “substituent” in the phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) which may have a substituent and the sulfamoyl group (H ₂ NSO ₂ —) which may have a substituent "Includes the above halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, and the like.

Moreover, as a substituent of the arylene group and 1,8-naphthylene group represented by Y and Z in General formula (1), you may have a halogen atom, the alkyl group which may have a substituent, and a substituent. Good alkoxyl group, aryl group which may have a substituent, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts, phthalimide which may have a substituent Examples thereof include a methyl group and a sulfamoyl group which may have a substituent, and these are synonymous with the substituents described in the above R ^{1 to} R ⁵ .

Among the above substituents, preferred substituents include a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent,- SO ₃ H, —COOH, a phthalimidomethyl group, a sulfamoyl group which may have a substituent, and a more preferable substituent include a halogen atom.

Furthermore, the quinophthalone compound used in the color filter colorant of the present invention is preferably any one of the general formulas (1A) to (1C). Here, in R ^{6 to} R ²⁰ , R ^{21 to} R ³⁷ and R ^{38 to} R ⁵² , a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, An aryl group which may have a substituent, —SO ₃ H; —COOH; and a monovalent to trivalent metal salt of these acidic groups; an alkyl ammonium salt, a phthalimidomethyl group which may have a substituent, or The sulfamoyl group which may have a substituent is synonymous with the group demonstrated by General formula (1).

R ^{11 to} R ¹⁴ in the general formula (1A) and / or R ^{49 to} R ^{52 in} the general formula (1C) adjacent to each other form an aromatic ring which may have a substituent. May be. The aromatic ring herein includes a hydrocarbon aromatic ring and a heteroaromatic ring. The hydrocarbon aromatic ring includes a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, and the heteroaromatic ring includes pyridine. And a ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring.

Further, the quinophthalone compound used in the colorant for color filter of the present invention is such that R ^{6 to} R ²⁰ , R ^{21 to} R ³⁷ , and R ^{38 to} R ^{52 in} the general formulas (1A) to (1C) are hydrogen atoms, halogens An atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, —SO ₃ H, —COOH, a phthalimidomethyl group, a substituent; It is more preferably a sulfamoyl group which may be present, and more preferably a hydrogen atom or a halogen atom.

  Specific examples of the quinophthalone compound used in the colorant for color filter of the present invention include the following quinophthalone compounds (a) to (t), but the present invention is not limited thereto.

<Method for producing quinophthalone compound>
The quinophthalone compound used in the present invention can be produced, for example, by the method described in Japanese Patent Publication No. 2930774. Hereinafter, a general method for producing the quinophthalone compound represented by the general formula (1) will be described. The phthalic anhydrides represented by the following general formula (3) or the naphthalic anhydrides represented by the following general formula (4) 2 to 1 equivalent of 8-aminoquinaldine represented by the following general formula (2) 3 equivalents are subjected to a condensation reaction in benzoic acid by heating at 160 to 200 ° C. in a nitrogen atmosphere. When making it react, before a reaction mixture reaches 160-200 degreeC, condensation for phthalic anhydride can be advanced by a two-step process by hold | maintaining at 120-160 degreeC for 1-3 hours.

Wherein, R ⁵³ to R ⁵⁷ have the same meanings as R ¹ to R ⁵ in the general formula (1). ]

[Wherein, R ^{58 to} R ⁶¹ and R ^{62 to} R ⁶⁷ have the same meanings as R ^{11 to} R ²⁰ , R ^{26 to} R ³⁷ , and R ^{43 to} R ^{52 in} the general formulas (1A) to (1C). ]

  In the reaction, phthalic anhydrides represented by the general formula (3) or naphthalic anhydrides represented by the general formula (4) are added to 1 equivalent of 8-aminoquinaldine represented by the general formula (2). After adding 1 to 2 equivalents and heating and stirring at 120 to 160 ° C. for 1 to 3 hours, phthalic anhydrides represented by general formula (3) having different structures or naphthalic anhydride represented by general formula (4) are added. By adding 1 to 2 equivalents and heating and condensing at 160 to 200 ° C., acid anhydrides having different structures on the amino group side and methyl group side of 8-aminoquinaldine can be condensed.

  Also, two or more structurally different quinophthalone compounds can be synthesized simultaneously by reacting 8-aminoquinaldine with two or more structurally different phthalic anhydrides or naphthalic anhydrides simultaneously. (Hereinafter referred to as “co-synthesis method”). For example, 1.8 equivalents of tetrachlorophthalic anhydride and 1.2 equivalents of other phthalic anhydrides are condensed with 1 equivalent of 8-aminoquinaldine to obtain C.I. I. Pigment Yellow 138 and a specific quinophthalone compound can be produced simultaneously.

  Moreover, according to the synthesis method of the compound (1) described in Patent Document 3, a compound of the following general formula (6) can be synthesized from a quinophthalone compound represented by the following general formula (5). Furthermore, the quinophthalone compound represented by the general formula (1C) is synthesized by condensing the naphthalic anhydrides represented by the general formula (6) and the general formula (4) in benzoic acid at 160 to 200 ° C. It is also possible. The manufacturing method of a quinophthalone compound is not limited to these methods.

[Wherein R ^{68 to} R ⁷² and R ^{81 to} R ⁸⁵ have the same meanings as R ^{38 to} R ⁴² in formula (1C), and R ^{73 to} R ⁸⁰ and R ^{86 to} R ⁸⁹ represent formula (1C). Are the same as R ^{43 to} R ⁵² in FIG. ]

  Moreover, according to the synthesis method of compound (1) described in Patent Document 3, a compound of the following general formula (7) can be synthesized from a quinophthalone compound represented by general formula (1A) or (1B). Furthermore, the general formula (7) and the phthalic anhydrides represented by the general formula (3) or the naphthalic anhydrides represented by the general formula (4) are condensed in benzoic acid at 160 to 200 ° C. It is also possible to synthesize a quinophthalone compound represented by the formula (1A) or (1B). The manufacturing method of a quinophthalone compound is not limited to these methods.

[Wherein R ^{90 to} R ⁹⁴ have the same meanings as R ^{6 to} R ¹⁰ in general formula (1A) or R ^{21 to} R ²⁵ in general formula (1B), and R ^{95 to} R ¹⁰⁰ represent general formula (1A). Are the same as R ^{15 to} R ²⁰ in R 1 or R ^{32 to} R ³⁷ in General Formula (1B). ]

  The colorant of the present invention may contain two or more quinophthalone compounds. At this time, quinophthalone compounds produced separately may be mixed together, or two or more quinophthalone compounds may be produced at the same time by a cosynthesis method and used as a colorant. When these separately prepared quinophthalone compounds are used, they may be simply mixed before the two pigments are dispersed, or may be pulverized and mixed by a salt milling process. In particular, C.I. I. When it contains CI Pigment Yellow 138, it is desirable to use it after being pulverized and mixed by a cosynthesis method or a salt milling process. C. having a quinophthalone skeleton I. Pigment Yellow 138 and the quinophthalone compound represented by the general formula (1) are pulverized and mixed together, so that fine particles are obtained and a high contrast ratio is obtained as compared with the case where each is subjected to salt milling alone. .

  The colored composition containing the quinophthalone compound of the present invention has a yellow hue itself, and when used in combination with other colorants, the yellow filter segment, green filter segment, and red filter segment of the same color are used. It can be set as the coloring composition for forming. Among these, the colored composition of the present invention can be used in combination with a green colorant and / or a blue colorant to obtain a colored composition used for a green filter segment having high brightness and high contrast.

  The coloring composition of the present invention may contain a yellow colorant other than the quinophthalone compound within a range not impairing the effects of the present invention for the purpose of adjusting the hue. Examples of the yellow colorant that can be used in the coloring composition of the present invention include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, It can be used yellow pigments such 82,185,187,188,192,193,194,196,198,199,213,214.

  In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, C.I. I. Pigment Yellow 138, 139, 150, and 185 are preferable, and C.I. I. Pigment Yellow 138 and 150 are more preferable, and C.I. I. Pigment Yellow 138 is particularly preferable.

  Furthermore, the coloring composition of the present invention may contain a green colorant and / or a blue colorant to form a green filter segment. Examples of the green colorant that can be used in the coloring composition of the present invention include C.I. I. And green pigments such as CI Pigment Green 7, 10, 36, 37, and 58. In particular, from the viewpoint of the brightness of the filter segment, C.I. I. Pigment Green 58 is preferable. Examples of blue colorants that can be used in the coloring composition of the present invention include C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, or blue pigments such as aluminum phthalocyanine pigments. In particular, an aluminum phthalocyanine pigment is mentioned from the viewpoint of the brightness of the filter segment.

<Miniaturization of pigment>
The quinophthalone compound used in the color filter colorant of the present invention may exhibit pigment properties depending on the type of substituent. When the quinophthalone compound exhibits the properties of a pigment, it can be suitably used as a colorant for a color filter by refining the pigment particles by a method such as salt milling. The primary particle diameter of the pigment is preferably 10 nm or more, but in order to form a filter segment with high contrast, it is preferably 80 nm or less. A particularly preferred range is 20 to 60 nm.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight based on the total weight of the pigment (100% by weight) from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 2 to 200% by weight based on the total weight of the pigment (100% by weight).

<Coloring composition for color filter>
The coloring composition for a color filter of the present invention is composed of a binder resin and an organic solvent in addition to the colorant described above.
<Binder resin>
Examples of the binder resin contained in the colored composition of the present invention include conventionally known thermoplastic resins and thermosetting resins.
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

  When used as a coloring composition for a color filter, the spectral transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, aldehyde groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. In addition, polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer are half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferred as the color filter coloring composition.

  The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene (Meth) acrylates such as lenglycol (meth) acrylate, or (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, dye (Meth) acrylamides such as acetone (meth) acrylamide or acryloylmorpholine, styrenes such as styrene or α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether Examples include vinyl ethers, vinyl acetate, and fatty acid vinyls such as vinyl propionate.

  Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-sc N-imidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

  In particular, it is preferable to have a structural unit derived from an N-substituted maleimide, and among them, cyclohexylmaleimide, methylmaleimide, ethylmaleimide, and 1,2-bismaleimideethane are preferable from the viewpoint of heat resistance, and cyclohexylmaleimide is particularly preferable.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.
The colored composition of the present invention preferably contains a thermosetting resin in terms of heat resistance, for example, among them, an epoxy resin and a melamine resin can be more suitably used, and a melamine resin is particularly preferable, A melamine compound having a methylolimino group or a condensate thereof is more preferable.

  The thermosetting resin is preferably added in the range of 5 to 60 parts by weight with respect to 100 parts by weight of the colorant. If the amount is less than 10 parts by weight, the effect of improving heat resistance and light resistance is reduced, and if it exceeds 60 parts by weight, the developability deteriorates during alkali development, which is not preferable.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 8,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 50,000, and the value of Mw / Mn is preferably 10 or less.
Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are connected to four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by the company and using tetrahydrofuran as the mobile phase.

  When using a binder resin as a color composition for a color filter, from the viewpoint of pigment dispersibility, developability, and heat resistance, a carboxyl group, a pigment carrier, and a solvent that act as a pigment adsorbing group and an alkali-soluble group during development. The balance between the aliphatic group and the aromatic group acting as an affinity group for is important for pigment dispersibility, developability, and durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin can be used in an amount of 20 to 500% by weight based on the total weight of the colorant. If it is less than 30% by weight, the film formability and various resistances are insufficient, and if it exceeds 500% by weight, the pigment concentration is low and color characteristics cannot be expressed.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent can be included to facilitate the formation.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Methylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol mono Ethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  Among them, because of good dispersion of the colorant of the present invention, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, benzyl It is preferable to use aromatic alcohols such as alcohol and ketones such as cyclohexanone.

  An organic solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment with a desired uniform film thickness, the total weight of the colorant is 100% by weight (500% to 4000% by weight). It is preferable to use it in the quantity.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.

<Dye derivative>
Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more. When a pigment derivative is used, one having a quinophthalone skeleton is preferable from the viewpoints of brightness and dispersibility.

  The blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, most preferably based on the total amount of the additive colorant (100% by weight) from the viewpoint of improving the dispersibility of the additive colorant. Preferably it is 3 weight% or more. Further, from the viewpoint of heat resistance and light resistance, the total amount of the additive pigment is preferably 40% by weight or less, more preferably 35% by weight or less, based on the total amount (100% by weight).

<Resin type dispersant>
The resin-type dispersant has a colorant affinity part that has the property of adsorbing to the added colorant, and a part that is compatible with the colorant carrier, and adsorbs to the added colorant to disperse in the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

Among the above dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion is lowered and a high contrast ratio is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer or side chain is preferable. A nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, and the like are preferable.
The resin-type dispersant is preferably used in an amount of about 5 to 200% by weight relative to the total amount of the pigment, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

<Surfactant>
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The compounding amount in the case of adding the resin type dispersant and the surfactant is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight based on the total amount of the added colorant (100% by weight). %. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is adversely affected by the excessive dispersant. May affect.

<Method for producing colored composition>
The coloring composition of the present invention comprises a mixture of a colorant containing at least the quinophthalone compound represented by the general formula (1), a binder resin, and an organic solvent, a three-roll mill, a two-roll mill, a sand mill, a kneader, Alternatively, it can be produced by finely dispersing using various dispersing means such as an attritor. Moreover, the coloring composition of this invention can also be manufactured by mixing what disperse | distributed the coloring agent etc. finely in binder resin and the organic solvent separately.

  In this way, when the colorant refined to an average primary particle size of 100 nm or less is dispersed in a transparent resin using a dispersing machine such as a sand mill, it is in a state of dispersed particles composed of secondary particles in which a plurality of primary particles are collected. Dispersed, the dispersed particles gradually become smaller with the progress of the dispersed state, and finally become dispersed in the state of primary particles, but the dispersed state is controlled by the size of the dispersed particles, The dispersed particles are dispersed so that the average diameter is in the range of 50 nm to 150 nm.

  As the dispersion progresses, the dispersed particle diameter becomes smaller, the transparency increases, and the contrast ratio rises. Therefore, the smaller the dispersed particle diameter is, the better the contrast ratio can be obtained from about 300 nm. On the other hand, when the dispersion progresses and the dispersed particle size becomes small, the viscosity of the dispersion increases and the thixotropic property tends to increase. When used as a coloring composition for a color filter, it is required that a thin film is applied and the surface of the coating film is smooth, so that it has a low viscosity and a Newtonian flow. For this reason, it is preferable to suppress the dispersed particle size to about 100 nm in consideration of the viscosity and thixotropic property preferable for normal use. Thus, by using a colorant having an average primary particle size of 100 nm or less and controlling the degree of dispersion so that the average particle size of the dispersed particles is in the range of 50 nm to 150 nm, the increase in viscosity and thixotropic property are minimized. A pigment dispersion with a very high contrast ratio can be obtained.

<Removal of coarse particles>
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

  The coloring composition of the present invention can be used as a coloring composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
The photopolymerizable monomer includes a monomer or oligomer that is cured by ultraviolet rays or heat to generate a transparent resin, and these can be used alone or in combination of two or more. The amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator>
The colored composition for a color filter of the present invention is a solvent development type or alkali development type colored resist material added with a photopolymerization initiator or the like when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method. It can be prepared in the form of The blending amount when using the photopolymerization initiator is preferably 2 to 200% by weight based on the total amount of the colorant, and 5 to 150% by weight from the viewpoint of photocurability and developability. More preferred.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-meth) Cyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxy) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 2 to 200% by weight based on the total amount of the colorant in the color filter coloring composition (100% by weight), and 5 from the viewpoint of photocurability and developability. More preferably, it is -150 weight%.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer. Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophen Non, 4,4′-diethylaminobenzophenone and the like.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the colored composition (100% by weight). From the viewpoint of developability, it is more preferably 5 to 50% by weight.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group and low solubility in water, and when added to a coloring composition, It has the feature that its surface tension lowering ability is low, and it is useful to have good wettability to the glass plate despite its low surface tension lowering ability, and the added amount that does not cause coating film defects due to foaming In this case, those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used. Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01 to 15 weight% is preferable with respect to the thermosetting resin whole quantity.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant in the coloring composition (100% by weight).

<Color filter>
Next, the color filter of the present invention will be described. The color filter of this invention comprises the filter segment formed using the coloring composition for color filters of this invention. Examples of the color filter include those having a red filter segment, a green filter segment, and a blue filter segment. The filter segment is coated with a color filter coloring composition by a spin coat method or a die coat method, and then ultraviolet rays or the like. The active energy rays are irradiated to cure the portion that becomes the filter segment, and then developed to form on the substrate.

  The coloring composition for a color filter of the present invention is mainly used for forming a green filter segment, and the filter segments of other colors may be formed using a conventionally used red coloring composition and blue coloring composition. it can. The colored composition of each color other than the colored composition for color filter of the present invention can be formed using each colored composition containing each color pigment, the binder resin, the photopolymerizable composition, and the like.

  The red filter segment can be formed using a red coloring composition including a red pigment and a pigment carrier. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, Red pigments such as 281, 282, 283, 284, 285, 286, or 287 are used. Further, a basic dye or a salt-forming compound of an acid dye exhibiting a red color can also be used.

  The red coloring composition includes C.I. I. Pigment orange 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213, or may be used in combination of a yellow pigment 214, and the like.

  Examples of the blue coloring composition include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like are used, and C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination. Further, a basic dye or a salt forming compound of an acidic dye that exhibits blue or purple can be used.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, etc. in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “parts” means “parts by mass” unless otherwise specified. First, prior to Examples, the method for measuring the average primary particle size of the colorant of the present invention, the method for identifying the quinophthalone compound in the colorant, the dye derivative (1) used in the color composition of the present invention, the blue colorant The manufacturing method of 1 (B-1) will be described.

(Measurement method of average primary particle size of colorant)
The average primary particle diameter of the colorant was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the short axis diameter and the long axis diameter of the primary particles of each colorant were measured, and the average was used as the particle diameter of the colorant primary particles. Next, for 100 or more colorant particles, the volume (weight) of each particle was determined by approximating the determined particle size cube, and the volume average particle size was defined as the average primary particle size.

(Method for identifying quinophthalone compound in colorant)
Identification of the quinophthalone compound in the colorant of the present invention is obtained by calculation using the MALDI mass spectrometer autoflex III (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonics, and the molecular ion peak of the obtained mass spectrum. Identified with agreement with mass number.

(Production of pigment derivative (1))
According to the synthesis method described in Japanese Patent No. 4585781, a pigment derivative (1) was obtained.

(Production of blue colorant 1 (B-1))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine (AlPc-Cl). Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water, and dried to obtain 102 parts of hydroxyaluminum phthalocyanine (AlPc-OH).

  Subsequently, 100 parts of hydroxyaluminum phthalocyanine (AlPc-OH), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of a colorant (B-1) were obtained. The average primary particle size was 31.2 nm.

[Example 1]
(Production of yellow colorant 1 (Y-1))
Compound (1) was obtained according to the synthesis method described in JP-A-2008-81666.

  To 300 parts of methyl benzoate, 100 parts of compound (1), 70 parts of 1,8-naphthalic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. The formation of the quinophthalone compound (a) and the disappearance of the starting compound (1) were confirmed by TOF-MS. Further, after cooling to room temperature, the reaction mixture was added to 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 130 parts of quinophthalone compound (a). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (a).

  Next, 100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 1 (Y-1) were obtained. The average primary particle size was 31.5 nm.

[Example 2]
(Production of yellow colorant 2 (Y-2))
70 parts of quinophthalone compound (a), C.I. I. 30 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of yellow colorant 2 (Y-2) were obtained. The average primary particle size was 30.6 nm.

[Example 3]
(Production of yellow colorant 3 (Y-3))
70 parts of quinophthalone compound (a) and C.I. I. 30 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF) was added to 50 parts of quinophthalone compound (a) and C.I. I. Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”) was changed to 50 parts except that Yellow Colorant 2 (Y-2) was produced. Obtained. The average primary particle size was 29.4 nm.

[Example 4]
(Production of yellow colorant 4 (Y-4))
70 parts of quinophthalone compound (a) and C.I. I. 30 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF) was added to 20 parts of Cinophthalone Compound (a) and C.I. I. Pigment Yellow 138 ("Pariotol Yellow K0960-HD" manufactured by BASF) was changed to 80 parts except that Yellow Colorant 2 (Y-2) was produced. Obtained. The average primary particle size was 31.3 nm.

[Example 5]
(Production of yellow colorant 5 (Y-5))
Preparation of yellow colorant (Y-1) except that 70 parts of 1,8-naphthalic anhydride was changed to a mixture of 42 parts of 1,8-naphthalic anhydride and 60 parts of tetrachlorophthalic anhydride; In the same manner, yellow colorant 5 (Y-5) comprising a mixture of quinophthalone compound (a) and Pigment Yellow 138 was obtained. The average primary particle size was 27.9 nm. As a result of the TOF-MS measurement, the composition ratio of the quinophthalone compound (a) and the pigment yellow 138 in the yellow colorant 5 was 5: 5.

[Example 6]
(Production of yellow colorant 6 (Y-6))
To 200 parts of methyl benzoate, 35 parts of 8-aminoquinaldine, 33 parts of 1,8-naphthalic anhydride, 47 parts of tetrachlorophthalic anhydride and 154 parts of benzoic acid are added and heated to 160 ° C. for 2 hours. Stirring was performed. Subsequently, 95 parts of tetrachlorophthalic anhydride and 50 parts of benzoic acid were added and stirred at 180 ° C. for 3 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 6140 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 125 parts of a quinophthalone compound. As a result of TOF-MS measurement, it was confirmed that the yellow colorant 6 was composed mainly of a composition ratio of about 5: 5 between the quinophthalone compound (a) and Pigment Yellow 138. Further, a very small amount of molecular ion peak corresponding to the mass number of the quinophthalone compound (c) was observed, suggesting that a very small amount of the quinophthalone compound (c) was contained.

  Subsequently, 100 parts of the obtained quinophthalone compound, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of Colorant 6 (Y-6) were obtained. The average primary particle size was 29.2 nm.

[Example 7]
(Production of yellow colorant 7 (Y-7))
To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 115 parts of 1,8-naphthalic anhydride and 154 parts of benzoic acid were added, heated to 180 ° C., and stirred for 4 hours. Further, after cooling to room temperature, the reaction mixture was added to 5440 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 119 parts of quinophthalone compound (c). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (c).

  Subsequently, 100 parts of the obtained quinophthalone compound (c), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of yellow colorant 7 (Y-7) were obtained. The average primary particle size was 34.7 nm.

[Example 8]
(Production of yellow colorant 8 (Y-8))
Using the quinophthalone compound (c) as a raw material, the compound (2) was obtained by the same method as the synthesis of the compound (1) according to the synthesis method described in JP-A-2008-81666.

  To 300 parts of methyl benzoate, 100 parts of compound (2), 102 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. The formation of the quinophthalone compound (b) and the disappearance of the starting compound (2) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 170 parts of quinophthalone compound (b). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (b).

  Subsequently, 100 parts of the obtained quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 8 (Y-8) were obtained. The average primary particle size was 31.2 nm.

[Example 9]
(Production of yellow colorant 9 (Y-9))
Except having changed 70 parts of quinophthalone compounds (a) into 70 parts of quinophthalone compounds (b), it carried out similarly to manufacture of the yellow coloring agent 2 (Y-2), and obtained the yellow coloring agent 9 (Y-9). . The average primary particle size was 30.8 nm.

[Example 10]
(Production of yellow colorant 10 (Y-10))
Except having changed 50 parts of quinophthalone compounds (a) into 50 parts of quinophthalone compounds (b), it carried out similarly to manufacture of the yellow coloring agent 3 (Y-3), and obtained the yellow coloring agent 10 (Y-10). . The average primary particle size was 30.1 nm.

[Example 11]
(Production of yellow colorant 11 (Y-11))
Except having changed 20 parts of quinophthalone compounds (a) into 20 parts of quinophthalone compounds (b), it carried out similarly to manufacture of the yellow coloring agent 4 (Y-4), and obtained the yellow coloring agent 11 (Y-11). . The average primary particle size was 29.9 nm.

[Example 12]
(Production of yellow colorant 12 (Y-12))
To 200 parts of methyl benzoate, 35 parts of 8-aminoquinaldine, 38 parts of tetrachlorophthalic anhydride and 154 parts of benzoic acid were added, heated to 160 ° C., and stirred for 2 hours. Subsequently, 32 parts of tetrachlorophthalic anhydride, 26 parts of 1,8-naphthalic anhydride and 50 parts of benzoic acid were added and stirred at 180 ° C. for 3 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 6140 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 125 parts of a quinophthalone compound. As a result of TOF-MS measurement, it was confirmed that the yellow colorant 6 was composed mainly of a composition ratio of about 5: 5 between the quinophthalone compound (b) and pigment yellow 138. Further, a very small amount of molecular ion peak corresponding to the mass number of the quinophthalone compound (c) was observed, suggesting that a very small amount of the quinophthalone compound (c) was contained.

  Subsequently, 100 parts of the obtained quinophthalone compound, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of colorant 12 (Y-12) were obtained. The average primary particle size was 29.3 nm.

[Example 13]
(Production of yellow colorant 13 (Y-13))
The yellow quinophthalone compound (d) was prepared in the same manner as in the production of yellow colorant 8 (Y-8) except that 102 parts of tetrachlorophthalic anhydride was changed to 70 parts of 2,3-naphthalenedicarboxylic anhydride. Colorant 13 (Y-13) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (d). The average primary particle size was 31.6 nm.

[Example 14]
(Production of yellow colorant 14 (Y-14))
To 200 parts of methyl benzoate, 35 parts of 8-aminoquinaldine, 46 parts of 1,8-naphthalic anhydride, and 154 parts of benzoic acid were added, heated to 160 ° C., and stirred for 2 hours. Subsequently, 46 parts of 2,3-naphthalenedicarboxylic acid anhydride and 50 parts of benzoic acid were added and stirred at 180 ° C. for 3 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 6140 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 104 parts of a quinophthalone compound (e). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (e).

  Subsequently, 100 parts of the obtained quinophthalone compound (e), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of colorant 14 (Y-14) were obtained. The average primary particle size was 31.8 nm.

[Example 15]
(Production of yellow colorant 15 (Y-15))
Except for changing 102 parts of tetrachlorophthalic anhydride to 70 parts of 1,2-naphthalic anhydride, the same procedure as in the production of yellow colorant 8 (Y-8) was carried out, and the yellow coloration which is the quinophthalone compound (f) Agent 15 (Y-15) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (f). The average primary particle size was 31.9 nm.

[Example 16]
(Production of yellow colorant 16 (Y-16))
Except for changing 102 parts of tetrachlorophthalic anhydride to 165 parts of tetrabromophthalic anhydride, the same procedure as in the production of yellow colorant 8 (Y-8) was carried out, and yellow colorant 15 (Y) as the quinophthalone compound (g) -15) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (g). The average primary particle size was 30.9 nm.

[Example 17]
(Production of yellow colorant 17 (Y-17))
To 200 parts of methyl benzoate, 35 parts of 8-aminoquinaldine, 46 parts of 1,8-naphthalic anhydride, and 154 parts of benzoic acid were added, heated to 160 ° C., and stirred for 2 hours. Subsequently, 113 parts of tetrabromophthalic anhydride and 50 parts of benzoic acid were added and stirred at 180 ° C. for 3 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 6140 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 162 parts of a quinophthalone compound (h). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (h).

  Subsequently, 100 parts of the obtained quinophthalone compound (h), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of colorant 17 (Y-17) were obtained. The average primary particle size was 31.2 nm.

[Example 18]
(Production of yellow colorant 18 (Y-18))
To 200 parts of methyl benzoate, 35 parts of 8-aminoquinaldine, 70 parts of tetrachlorophthalic anhydride and 154 parts of benzoic acid were added, heated to 160 ° C., and stirred for 2 hours. Subsequently, 99 parts of hexachloro-1,8-naphthalic anhydride and 50 parts of benzoic acid were added and stirred at 180 ° C. for 3 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 6140 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 168 parts of quinophthalone compound (i). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (i).

  Subsequently, 100 parts of the obtained quinophthalone compound (i), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of colorant 18 (Y-18) were obtained. The average primary particle size was 30.8 nm.

[Example 19]
(Production of yellow colorant 19 (Y-19))
To 200 parts of methyl benzoate, 35 parts of 8-aminoquinaldine, 163 parts of hexabromo-1,8-naphthalic anhydride, and 154 parts of benzoic acid were added, heated to 160 ° C., and stirred for 2 hours. Subsequently, 36 parts of phthalic anhydride and 50 parts of benzoic acid were added and stirred at 180 ° C. for 3 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 6140 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 195 parts of a quinophthalone compound (j). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (j).

  Subsequently, 100 parts of the obtained quinophthalone compound (j), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of colorant 19 (Y-19) were obtained. The average primary particle size was 31.1 nm.

[Example 20]
(Production of yellow colorant 20 (Y-20))
52 parts of the quinophthalone compound (b) was dissolved in 428 parts of 98% sulfuric acid and 472 parts of 25% fuming sulfuric acid and stirred at 85 ° C. for 2 hours to carry out sulfonation reaction. Next, this reaction solution was dropped into 6000 parts of ice water, and the precipitated quinophthalone compound was separated and washed with water to obtain a paste. The obtained paste was redispersed in 8000 parts of water and stirred at room temperature for 1 hour. After filtering off and washing with water, it was dried overnight at 80 ° C. to obtain 54 parts of a quinophthalone compound (k). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (k).

  Subsequently, 50 parts of the obtained quinophthalone compound (k) and C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 95 parts of yellow colorant 20 (Y-20) were obtained. The average primary particle size was 35.3 nm.

[Example 21]
(Production of yellow colorant 21 (Y-21))
52 parts of the quinophthalone compound (b) was dissolved in 428 parts of 98% sulfuric acid and 472 parts of 25% fuming sulfuric acid and stirred at 85 ° C. for 2 hours to carry out sulfonation reaction. Next, this reaction solution was dropped into 6000 parts of methyl ethyl ketone, the precipitated quinophthalone compound was filtered off, and washed with 4000 parts of methyl ethyl ketone to obtain a paste. The obtained paste was dissolved in 720 parts of chlorosulfonic acid, 15 parts of thionyl chloride was added dropwise over 1 hour while maintaining at 55 ° C., and the mixture was further stirred for 30 minutes. Subsequently, this reaction solution was dispersed in 5000 parts of ice water maintained at 5 ° C. or lower and stirred for 1 hour. The precipitated quinophthalone compound was filtered off, washed with 4000 parts of water, dispersed in a 15% diethylaminoethylamine aqueous solution, stirred at room temperature for 2 hours, and then stirred at 80 ° C. for 2 hours. After separation by filtration and washing with water, it was dried overnight at 80 ° C. to obtain 62 parts of quinophthalone compound (l). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (l).

  Subsequently, 50 parts of the obtained quinophthalone compound (l) and C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 95 parts of yellow colorant 21 (Y-21) were obtained. The average primary particle size was 33.4 nm.

[Example 22]
(Production of yellow colorant 22 (Y-22))
To 200 parts of methyl benzoate, 45 parts of 6-ethoxy-8-aminoquinaldine, 46 parts of 1,8-naphthalic anhydride and 154 parts of benzoic acid were added, heated to 160 ° C., and stirred for 2 hours. Subsequently, 70 parts of tetrachlorophthalic anhydride and 50 parts of benzoic acid were added and stirred at 180 ° C. for 3 hours. Furthermore, after cooling to room temperature, the reaction mixture was added to 6140 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 133 parts of a quinophthalone compound (m). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (m).

  Subsequently, 100 parts of the obtained quinophthalone compound (m), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 97 parts of colorant 22 (Y-22) were obtained. The average primary particle size was 32.1 nm.

[Example 23]
(Production of yellow colorant 23 (Y-23))
The quinophthalone compound was prepared in the same manner as in the production of the yellow colorant 22 (Y-22) except that 45 parts of 6-ethoxy-8-aminoquinaldine was changed to 54 parts of 6-trifluoromethyl-8-aminoquinaldine. A yellow colorant 23 (Y-23) as (n) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (n). The average primary particle size was 31.9 nm.

[Example 24]
(Production of yellow colorant 24 (Y-24))
The quinophthalone compound (o) was prepared in the same manner as in the production of the yellow colorant 22 (Y-22) except that 45 parts of 6-ethoxy-8-aminoquinaldine was changed to 52 parts of 6-phenyl-8-aminoquinaldine. Yellow colorant 24 (Y-24) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (o). The average primary particle size was 34.2 nm.

[Example 25]
(Production of yellow colorant 25 (Y-25))
Except for changing 45 parts of 6-ethoxy-8-aminoquinaldine to 59 parts of 6- (4-chlorophenyl) -8-aminoquinaldine, the same procedure as in the production of yellow colorant 22 (Y-22) was performed, Yellow coloring agent 25 (Y-25) which is a quinophthalone compound (p) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (p). The average primary particle size was 35.1 nm.

[Example 26]
(Production of yellow colorant 26 (Y-26))
Except for changing 102 parts of tetrachlorophthalic anhydride to 72 parts of 4-t-butylphthalic anhydride, the same procedure as in the production of yellow colorant 8 (Y-8) was performed, and the yellow coloration of quinophthalone compound (q) was obtained. Agent 26 (Y-26) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (q). The average primary particle size was 34.3 nm.

[Example 27]
(Production of yellow colorant 27 (Y-27))
The yellow colorant, which is the quinophthalone compound (r), was prepared in the same manner as in the production of the yellow colorant 8 (Y-8) except that 102 parts of tetrachlorophthalic anhydride was changed to 77 parts of 4-trifluorophthalic anhydride. 27 (Y-27) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (r). The average primary particle size was 32.6 nm.

[Example 28]
(Production of yellow colorant 28 (Y-28))
Except for changing 102 parts of tetrachlorophthalic anhydride to 68 parts of trimellitic anhydride, it was carried out in the same manner as in the production of yellow colorant 8 (Y-8), and yellow colorant 28 (Y) which is a quinophthalone compound (s) -28) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (s). The average primary particle size was 29.8 nm.

[Example 29]
(Production of yellow colorant 29 (Y-29))
44 parts of the quinophthalone compound (b) were dissolved in 540 parts of 95% sulfuric acid, 38 parts of N-hydroxymethylphthalimide was added thereto, and the mixture was stirred at 85 ° C. for 7 hours. After cooling, the reaction solution was dropped into 3600 parts of ice water, and the precipitated quinophthalone compound was separated and washed with water to obtain a paste. The obtained paste was redispersed in 5000 parts of water and stirred at room temperature for 1 hour. After filtration and washing with water, the precipitate was dried at 80 ° C. for a whole day and night to obtain 53 parts of a quinophthalone compound (t).
As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (t).

  Subsequently, 50 parts of the obtained quinophthalone compound (t) and C.I. I. 50 parts of Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 29 (Y-29) were obtained. The average primary particle size was 35.2 nm.

[Example 30]
(Production of Yellow Colorant 30 (Y-30))
C. I. 50 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF Corporation) I. Pigment Yellow 150 (“E4GN” manufactured by LANXESS) was used in the same manner as in the production of Yellow Colorant 3 (Y-3), except that Yellow Colorant 30 (Y-30) was obtained. The average primary particle size was 36.1 nm.

[Example 31]
(Production of yellow colorant 31 (Y-31))
C. I. 50 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF Corporation) I. Except for changing to 50 parts of Pigment Yellow 150 (“E4GN” manufactured by LANXESS), yellow colorant 31 (Y-31) was obtained in the same manner as in the production of yellow colorant 10 (Y-10). The average primary particle size was 36.2 nm.

[Comparative Example 1]
(Production of yellow colorant 32 (Y-32))
C. I. 100 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. . Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow colorant 32 (Y-32) were obtained. The average primary particle size was 35.8 nm.

[Comparative Example 2]
(Production of yellow colorant 33 (Y-33))
C. I. 100 parts of CI Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF Corporation) I. Except for changing to 100 parts of Pigment Yellow 150 (“E4GN” manufactured by LANXESS), yellow colorant 33 (Y-33) was obtained in the same manner as in the production of yellow colorant 32 (Y-32). The average primary particle size was 36.5 nm.

[Comparative Example 3]
(Production of yellow colorant 34 (Y-34))
C. I. 100 parts of CI Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF Corporation) I. 50 parts of Pigment Yellow 138 (BASF “Paliotol Yellow K0960-HD”) and C.I. I. Pigment Yellow 150 (“E4GN” manufactured by LANXESS) was used in the same manner as in the production of Yellow Colorant 32 (Y-32), except that the mixture was changed to a mixture with 50 parts of Yellow Colorant 34 (Y-34). . The average primary particle size was 37.2 nm.

The contents of the produced yellow colorants 1 to 34 (Y-1 to 34) are shown in Table 1. “PY138” and “PY150” described in Table 1 are C.I. I. Pigment yellow 138 and C.I. I. CI Pigment Yellow 150.

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

(Weight average molecular weight of binder resin)
The weight average molecular weight of the acrylic resin is a polystyrene equivalent weight average molecular weight measured by GPC (gel permeation chromatography).

<Preparation of yellow coloring composition>
[Example 32]
(Preparation of yellow coloring composition 1 (YP-1))
After stirring and mixing a mixture consisting of the following components uniformly, using a zirconia bead having a diameter of 0.5 mm, the mixture was dispersed for 5 hours in an Eiger mill (Eiger Japan “Mini Model M-250 MKII”). It filtered with a 5-micrometer filter and produced the yellow coloring composition 1 (YP-1).
Yellow colorant 1 (Y-1) 9.5 parts Dye derivative (1) 0.5 part Resin-type dispersant ("PB821" manufactured by Ajinomoto Fine Techno Co., Ltd.) 1.0 part Acrylic resin solution 1 45.0 parts Propylene glycol Monomethyl ether acetate 44.0 parts

[Examples 33 to 62, Comparative Examples 4 to 6]
(Production of yellow colored compositions 2-31, 40-42 (YP-2-31, 40-42))
Except having changed yellow coloring agent 1 (Y-1) into the yellow coloring agent of Table 2, it is the same as yellow coloring composition 1 (YP-1), and yellow coloring compositions 2-31, 40-42 (YP-2 to 31, 40 to 42) were prepared.

[Example 63]
(Preparation of yellow coloring composition 32 (YP-32))
After stirring and mixing a mixture consisting of the following components uniformly, using a zirconia bead having a diameter of 0.5 mm, the mixture was dispersed for 5 hours in an Eiger mill (Eiger Japan “Mini Model M-250 MKII”). It filtered with a 5 micrometers filter and produced the yellow coloring composition 32 (YP-32).

Yellow colorant 1 (Y-1) 10.0 parts Resin type dispersant (“PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.) 2.0 parts Acrylic resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate 40.0 parts

[Examples 64-70, Comparative Examples 7-9]
(Production of yellow coloring compositions 33 to 39, 43 to 45 (YP-33 to 39, 43 to 45))
The yellow coloring compositions 33 to 39 and 43 to 45 are the same as the yellow coloring composition 32 (YP-32) except that the yellow coloring agent 1 (Y-1) is changed to the yellow coloring agent described in Table 2. (YP-33 to 39, 43 to 45) were prepared.

<Evaluation of yellow coloring composition>
The yellow colored composition was evaluated by preparing a coating film using the yellow colored composition and measuring the brightness, film thickness, and contrast ratio. The evaluation method is shown below.
(Brightness evaluation)
The yellow coloring composition was applied onto a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and heated at 230 ° C. for 20 minutes to obtain a coating film. At this time, after the heat treatment at 230 ° C., the coating conditions (spin coater rotation speed and time) were appropriately changed so that the film thickness was x = 0.440 in the C light source. The lightness (Y) of the obtained coating film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), and judged according to the following criteria.
○: 89.0 or more Δ: 87.5 or more and less than 89.0 ×: less than 87.5

(Coloring power evaluation)
Using the same coating film as the one subjected to lightness evaluation, the film thickness when chromaticity of x (C) = 0.440 was measured was measured and judged according to the following criteria. It can be said that the smaller the film thickness that gives the chromaticity of x (C) = 0.440, the greater the coloring power, and the better.
○: Less than 2.0 [μm]
Δ: 2.0 or more and less than 3.0 [μm]
×: 3.0 or more [μm]

(Contrast ratio evaluation)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)

Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion. Using the same coating film as the one subjected to lightness evaluation, the determination was made according to the following criteria.
○: 3000 or more Δ: 2000 or more to less than 3000 ×: less than 2000

  Table 2 shows the evaluation results of the yellow coloring compositions prepared in Examples and Comparative Examples, together with the types of yellow coloring agents used in the yellow coloring composition.

  From Table 2, it is clear that the yellow colored compositions of Examples 32-70 using the quinophthalone compound represented by the general formula (1) as a colorant are excellent in brightness and contrast ratio and exhibit high coloring power. It was. On the other hand, the yellow coloring compositions of Comparative Examples 4 to 9 using a conventionally used yellow coloring agent are inferior in lightness, contrast ratio, and coloring power, and all of the lightness, contrast ratio, and coloring power. It was clarified that a result satisfying the above was not obtained.

  When the yellow coloring compositions of Examples 33 to 35 were compared, differences in brightness, contrast ratio, and coloring power were recognized by changing the ratio of the quinophthalone compound (a) and CI Pigment Yellow 138. As the ratio of the quinophthalone compound (a) was larger, the brightness and the coloring power tended to be higher, but the contrast ratio was about the yellow coloring composition of Example 34 (quinophthalone compound (a) /C.I. Pigment Yellow 138 = 5/5) showed the best results.

  Further, when the yellow coloring compositions of Examples 40 to 42 were compared, differences in brightness, contrast ratio, and coloring power were recognized by changing the ratio of the quinophthalone compound (b) and CI Pigment Yellow 138. . As the ratio of the quinophthalone compound (b) was larger, the brightness and the coloring power tended to be higher, but the contrast ratio was such that the yellow colored composition of Example 41 (quinophthalone compound (b) /C.I. Pigment Yellow 138 = 5/5) showed the best results.

  Comparing the yellow coloring compositions of Examples 34, 36 and 37, the quinophthalone compound (a) and C.I. I. It is clear that almost the same results can be obtained with the colorant obtained by separately synthesizing CI Pigment Yellow 138 and then mixing it during the salt milling process and the yellow colorant composition using the colorant obtained by the co-synthesis method. became.

  Example 32 and Example 63, Example 33 and Example 64, Example 34 and Example 65, Example 35 and Example 66, Example 39 and Example 67, Example 40 and Example 68, Example When comparing 41 and Example 69, and Example 42 and Example 70, respectively, it is clear that when the yellow coloring composition contains the pigment derivative (1), both the brightness and the contrast ratio are improved. It was.

<Preparation of green and blue coloring composition>
(Preparation of green coloring composition 1 (GP-1))
After stirring and mixing a mixture consisting of the following components uniformly, using a zirconia bead having a diameter of 0.5 mm, the mixture was dispersed for 5 hours in an Eiger mill (Eiger Japan “Mini Model M-250 MKII”). It filtered with a 5-micrometer filter and produced green coloring composition 1 (GP-1).
Green colorant 1 (CI Pigment Green 58) 10.0 parts Resin type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 45.0 parts Propylene glycol monomethyl ether acetate 44. 0 copies

(Preparation of blue colored composition 1 (BP-1))
The following mixture was stirred and mixed to be uniform, then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then a 5 μm filter. To give a green colored composition 2 (GP-2).


Blue colorant 1 (B-1) 10.0 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 45.0 parts Propylene glycol monomethyl ether acetate 44.0 parts

<Preparation of photosensitive coloring composition>
[Example 71]
(Preparation of photosensitive coloring composition 1 (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare photosensitive coloring composition 1 (GR-1).
Yellow colored composition 1 (YP-1) 18.4 parts Green colored composition 1 (GP-1) 26.6 parts Acrylic resin solution 2 4.5 parts Photopolymerizable monomer (“Aronix M402, manufactured by Toagosei Co., Ltd.) ] 3.6 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan) 1.3 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts ethylene glycol monomethyl ether Acetate 45.4 parts

[Examples 72 to 87, Comparative Examples 10 to 15]
(Preparation of photosensitive coloring compositions 2 to 23 (GR-2 to 23))
Using the yellow coloring composition shown in Table 3, and the green coloring composition or the blue coloring composition, and at the time of coating film evaluation, the chromaticity of x = 0.290 and y = 0.600 with a C light source The photosensitive coloring composition 1 (GR) except that the ratio of the yellow coloring composition and the green coloring composition or the blue coloring composition is changed so as to match (the ratio is changed so that the total amount of the coloring composition is 45 parts). In the same manner as in -1), photosensitive colored compositions 2 to 23 (GR-2 to 23) were prepared.

<Evaluation of coating film of photosensitive coloring composition>
Evaluation of the brightness, film thickness, and contrast ratio of the coating films prepared using the photosensitive coloring compositions 1 to 23 (GR-1 to 23) obtained was performed by the following methods.

(Brightness evaluation)
The photosensitive coloring composition is applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate by spin coating, then dried at 70 ° C. for 20 minutes, and ultraviolet rays are used at 300 mJ / cm ² using an ultrahigh pressure mercury lamp. It exposed and developed with the alkaline developing solution of 23 degreeC. As an alkaline developer, sodium carbonate 1.5% by weight, sodium bicarbonate 0.5% by weight, an anionic surfactant (“Perilox NBL” manufactured by Kao Corporation) 8.0% by weight, and water 90% by weight The thing which consists of was used. Furthermore, the coating film was obtained by heating at 230 degreeC for 30 minutes. Using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), the lightness (Y) of the obtained coating film was measured and judged according to the following criteria. In addition, the produced coating film was made to become the chromaticity (C light source) shown in Table 3 after the heat treatment at 230 ° C.
○: 59.5 or more Δ: 58.0 or more to less than 59.5 ×: less than 58.0

(Coloring power evaluation)
Using the same coating film as the one subjected to lightness evaluation, the film thickness when the chromaticity of x (C) = 0.290 and y (C) = 0.600 was measured was measured and judged according to the following criteria. The smaller the film thickness that gives the chromaticity of x (C) = 0.290 and y (C) = 0.600, the greater the coloring power, and the better.
○: Less than 2.5 [μm]
Δ: 2.5 or more and less than 3.0 [μm]
×: 3.0 or more [μm]

(Contrast ratio evaluation)
About the measuring method of the contrast ratio of a coating film, it measured by the method similar to the contrast ratio measurement of Examples 15-33 and Comparative Examples 4-9 of the yellow coloring composition. The contrast ratio was calculated using the same coating film that was evaluated for brightness, and judged according to the following criteria.
○: 3500 or more Δ: 3000 or more to less than 3500 ×: less than 3000

  Table 3 shows the evaluation results of the photosensitive coloring compositions prepared in Examples and Comparative Examples.

  From the results of Table 3, in the color filter formation, the examples using the photosensitive coloring composition containing the quinophthalone compound of the present invention satisfy all of the brightness, contrast ratio, and coloring power simultaneously as compared with the comparative example. It became clear that the result was obtained, and it was found that the brightness was particularly excellent.

<Production of color filter>
[Example 88]
The red photosensitive coloring composition 1 and the blue photosensitive coloring composition 1 used for preparation of the color filter were prepared. In addition, the photosensitive coloring composition 6 (GR-6) of this invention was used about green.

(Preparation of red coloring composition 1 (RP-1))
The mixture having the composition shown below was stirred and mixed uniformly, dispersed with picomil for 8 hours using zirconia beads having a diameter of 0.1 mm, filtered through a 5 μm filter, and red colored composition 1 (RP-1). Was made.
Red Colorant 1 (C.I. Pigment Red 254) 8.5 parts Red Colorant 2 (C.I. Pigment Red 177) 3.5 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 0 parts Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of red photosensitive coloring composition 1 (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a red photosensitive coloring composition 1 (RR-1).
Red coloring composition 1 (RP-1) 42.0 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907" manufactured by the company) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 39.6 parts ethylene glycol monomethyl ether acetate

(Preparation of blue coloring composition 2 (BP-2))
The mixture having the composition shown below is stirred and mixed uniformly, dispersed with picomil for 8 hours using zirconia beads having a diameter of 0.1 mm, filtered through a 5 μm filter, and blue colored composition 2 (BP-2) Was made.
Blue Colorant 2 (CI Pigment Blue 15: 6) 7.2 parts Purple Colorant 1 (CI Pigment Violet 23) 4.8 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of blue photosensitive coloring composition 1 (BR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive coloring composition 1 (BR-1).
Blue coloring composition 2 (BP-2) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd. 3.3 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

  A black matrix is patterned on a glass substrate, and a red photosensitive coloring composition 1 (RR-1) is applied onto the substrate with a film thickness such that x = 0.640 and y = 0.330 using a spin coater. A colored coating was formed. The coating was irradiated with 300 mJ / cm 2 of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. Formed. By the same method, the blue photosensitive coloring composition 1 (BR-6) of the present invention was formed to a thickness such that x = 0.290 and y = 0.600. -1) was used to apply film thicknesses such that x = 0.150 and y = 0.060, and green filter segments and blue filter segments were formed to obtain color filters.

  By using the photosensitive coloring composition 6 (GR-6) of the present invention, it was possible to produce a color filter having high brightness, high contrast, and excellent coloring power.

Claims (9)

A color filter colorant comprising a quinophthalone compound represented by the following general formula (1):

[In General Formula (1), R ^{1 to} R ⁵ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. An aryl group that may have, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts, phthalimidomethyl groups that may have a substituent, or substituents; Sulfamoyl group which may have, Y and Z are a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent , —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts, optionally substituted phthalimidomethyl groups, and optionally substituted sulfamoyl groups From the group of An arylene group optionally having a substituent, wherein at least one of Y and Z is a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, An aryl group which may have a substituent, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts, an optionally substituted phthalimidomethyl group, and 1 shows a 1,8-naphthylene group which may have a substituent selected from the group consisting of sulfamoyl groups which may have a substituent. ] The color filter colorant according to claim 1, wherein the quinophthalone compound is any one of the following general formulas (1A) to (1C).

[In the general formulas (1A) to (1C), R ^{6 to} R ²⁰ , R ^{21 to} R ³⁷ , and R ^{38 to} R ⁵² may each independently have a hydrogen atom, a halogen atom, or a substituent. An alkyl group, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts , A phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent, wherein adjacent groups of R ^{11 to} R ¹⁴ and R ^{49 to} R ⁵² are combined to form a substituent. An aromatic ring which may have a group may be formed. ] The colorant for color filter according to claim 2, wherein R ^{11 to} R ²⁰ , R ^{26 to} R ³⁷ , and R ^{43 to} R ⁵² are each independently a hydrogen atom or a halogen atom.   The color filter colorant according to claim 1, further comprising a yellow colorant.   The yellow colorant is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, and C.I. I. The colorant for color filter according to claim 4, wherein the colorant is at least one selected from CI Pigment Yellow 185.   A color composition for color filter comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant is the colorant according to any one of claims 1 to 5. Composition.   The color composition for color filters according to claim 6, further comprising a green colorant and / or a blue colorant.   Furthermore, the coloring composition for color filters of Claim 6 or 7 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter comprising at least one red filter segment, at least one green filter segment and at least one blue filter segment, wherein at least one green filter segment is formed by the color filter coloring composition according to claim 6-8. Color filter.